Alkylphenols in marine environments: Distribution monitoring strategies and detection considerations

The presence of alkylphenols (APs) in coastal and marine ecosystems is not as well-documented as it is in freshwater ecosystems. This paper reviews reported concentrations of alkylphenol ethoxylates (APEOs) and APs in seawater, sediments and organisms of marine environments such as estuaries, coastal lagoons, bights, harbours or deep sea in order to study their distribution. Overall contamination of marine aquatic compartments by APs and APEOs has been observed, while coastal areas in the vicinity of wastewater discharges are more impacted than deep sea environments, but to a lesser extent than freshwater sites. Sediments act as sinks for APs and APEOs, especially around wastewater discharge sites. Reported AP concentrations in marine organisms are higher in bivalves and gastropods than in fishes. As nonylphenols and octylphenols are estrogenomimetic, biological responses induced in marine organisms are discussed. Finally, we describe the cell bioassay approach for the biodetection of APs.     

Chemical composition of organic and mineral substances in silt bottom sediments of non-contaminated water bodies

Results of studying group and constituent composition of natural organic and mineral substances in silt bottom sediments of non-contaminated freshwater bodies are presented. The chemical composition of the investigated bottom sediments is shown to be complicated, diverse, and include products of autochthonous and allochthonous substance transformation. The necessity of further studying the concentrations of nutrients found in the bottom sediments of non-contaminated freshwater bodies, regarded as the “background” in estimating their environmental state, in studying processes occurring within water bodies, in determining natural and anthropogenic components of mineral and organic substances, as well as in estimating the balneologic value of the water bodies in question is substantiated.     

Coprostanols in Antarctic marine sediments: A biomarker for marine mammals and not human pollution

The first analysis of sterols in Antarctic marine sediment cores (Bransfield Strait and McMurdo Sound) is reported here. The isolated sterols in the sediments from Bransfield Strait are comprised mainly of dinosterol (4,23,24-trimethyl-5cholest-22-en-3β-ol), coprostanol (5β-cholestan-3β-ol) and epicoprostanol (5β-cholestan-3-ol) and trace amounts of cholesterol (cholest-5-en-3β-ol). The sediment cores of McMurdo Sound also contain small quantities of coprostanols in addition to large amounts of marine sterols. Dinosterol is a known dinoflagellate chemical marker, whereas coprostanols are currently being used as tracers for sewage contamination. However, sterol composition in Antarctic sediments is expected to be atypical of sewage input and probably different from those of temperate and tropical zones. The coprostanols must therefore arise from the feces of marine mammals, most probably whales which use the region for feeding and spawning. Based on the results of this study, caution should be exercised in the use of coprostanol to estimate the amount of sewage-derived organic matter transported away from impacted coastal areas.     

The use of diatom assemblages as ecological indicators in highly stratified estuaries and evaluation of existing diatom indices

Diatom indices are used to evaluate the ecological status of rivers but they have been rarely applied in estuaries. This study aimed to identify the diatom species indicating the main environmental gradients and pressures in a highly stratified estuary; and to evaluate the applicability of existing freshwater diatom indices. Marine influence due to salt-wedge intrusion and sea water mixing appeared as the main factor affecting diatom community. Three diatom assemblages were identified: indicators of riverine conditions (without marine influence), indicators of estuarine conditions (heterogeneous conditions with higher conductivities due to marine influence) and those specifically indicating well-established salt-wedge situations. Nowadays, the main human pressure affecting diatom community in the Ebro Estuary is the hydrological alteration resulting from flow regulation and abstraction. Several limitations were encountered in the application of diatom indices (e.g. inverse response with nutrients; ecologically important species not considered). Therefore, their use in estuaries should be done cautiously.     

Mineralization and magnetization of chiton teeth: paleomagnetic,sedimentologic, and biologic implications of organic magnetite

Magnetite precipitation and tooth formation in chitons (Polyplacophora) proceeds through a biochemically-controlled reduction of the mineral ferrihydrite. Resulting crystals of single-domain magnetite are closely packed against one another and are typically near 0.1 μm in diameter. The natural magnetization of these teeth is characterized by abnormally low stability to alternating field demagnetization (m.d.f. near 12 mT) but has no appreciable decay due to low-temperature cycling. Chitons may be responsible for natural magnetizations on the order of 10^?6 G in marine sediments, whereas mud bacteria could produce remanence near 10^?8 G in both marine and freshwater sediments.     

Marine risk assessment: linear alkylbenzenesulponates (LAS) in the North Sea

The fate of linear alkylbenzenesulponates (LAS) in estuaries and coastal areas of the North Sea has been characterized with simple environmental models. The predicted concentration range in the estuaries around the North Sea (0.9-9 microg LAS l(-1)) was validated by monitoring data (1-9 microg LAS l(-1)). In offshore sites of the North Sea, it is estimated--and experimentally verified for a few sites--that the LAS concentration is below analytical detection limit (i.e., 0.5 microg LAS l(-1)). The effects of LAS on marine organisms have been reviewed. For short-term acute tests, there was no significant difference (p = 0.83) between the mean LC50 values of freshwater and marine organisms (mainly pelagic species tested, 4.1 and 4.3 mg LAS l(-1), respectively). For longer-term chronic tests, it appeared that the sensitivity (mean no-observed effect concentration (NOEC) value) of marine and freshwater organisms (0.3 and 2.3 mg LAS l(-1), respectively) was significantly different pt-test = 0.007). The predicted no-effect-concentrations (PNEC) were 360 and 31 microg LAS l(-1), for freshwater and marine pelagic communities, respectively. Given that the maximum expected estuarine and marine concentrations are 3 to > 30 times lower than the PNEC, the risk of LAS to pelagic organisms in these environments is judged to be low.     

Applications of C and N stable isotopes to ecological and environmental studies in seagrass ecosystems

Stable isotopes of carbon and nitrogen are increasingly used in marine ecosystems, for ecological and environmental studies. Here, we examine some applications of stable isotopes as ecological integrators or tracers in seagrass ecosystem studies. We focus on both the use of natural isotope abundance as food web integrators or environmental tracers and on the use of stable isotopes as experimental tools. As ecosystem integrators, stable isotopes have helped to elucidate the general structure of trophic webs in temperate, Mediterranean and tropical seagrass ecosystems. As environmental tracers, stable isotopes have proven their utility in sewage impact measuring and mapping. However, to make such environmental studies more comprehensible, future works on understanding of basic reasons for variations of N and C stable isotopes in seagrasses should be encouraged. At least, as experimental tracers, stable isotopes allow the study of many aspects of N and C cycles at the scale of a plant or at the scale of the seagrass ecosystem.     

An overview of toxicant identification in sediments and dredged materials

The identification of toxicants affecting aquatic benthic systems is critical to sound assessment and management of our nation's waterways. Identification of toxicants can be useful in designing effective sediment remediation plans and reasonable options for sediment disposal. Knowledge of which contaminants affect benthic systems allows managers to link pollution to specific dischargers and prevent further release of toxicant(s). In addition, identification of major causes of toxicity in sediments may guide programs such as those developing environmental sediment guidelines and registering pesticides, while knowledge of the causes of toxicity which drive ecological changes such as shifts in benthic community structure would be useful in performing ecological risk assessments. To this end, the US Environmental Protection Agency has developed tools (toxicity identification and evaluation (TIE) methods) that allow investigators to characterize and identify chemicals causing acute toxicity in sediments and dredged materials. To date, most sediment TIEs have been performed on interstitial waters. Preliminary evidence from the use of interstitial water TIEs reveals certain patterns in causes of sediment toxicity. First, among all sediments tested, there is no one predominant cause of toxicity; metals, organics, and ammonia play approximately equal roles in causing toxicity. Second, within a single sediment there are multiple causes of toxicity detected; not just one chemical class is active. Third, the role of ammonia is very prominent in these interstitial waters. Finally, if sediments are divided into marine or freshwater, TIEs perforMed on interstitial waters from freshwater sediments indicate a variety of toxicants in fairly equal proportions, while TIEs performed on interstitial waters from marine sediments have identified only ammonia and organics as toxicants, with metals playing a minor role. Preliminary evidence from whole sediment TIEs indicates that organic compounds play a major role in the toxicity of marine sediments, with almost no evidence for either metal or ammonia toxicity. However, interpretation of these results may be skewed because only a small number of interstitial water (n = 13) and whole sediment (n = 5) TIEs have been completed. These trends may change as more data are collected.     

Tracing the anthropogenic lead sources in coastal sediments of SE-pacific (36 degrees Lat. S) using stable lead isotopes

This study evaluates the main sources of antropogenic Pb in one of the most industrialized centers of the southern Chilean coast (36 degrees S). Stable lead isotopes ((206)Pb/(207)Pb, (208)Pb/(207)Pb) were used to trace main Pb sources to coastal sediments, considering the suspended particulate matter (SPM) from marine (traps), continental (rivers) and industrial effluents, sediments and leaded gasoline samples. The atmospheric input was evaluated through natural collectors; i.e. Raqui-Tubul salt marsh. Results show that marine samples lie on a trend between industrial effluents ( approximately 1.16, 2.44) and natural sources (1.20, 2.50), not related to gasoline consumption. Salt marsh sediments show comparable isotopic composition to marine samples, suggesting the importance of the atmospheric input in the coastal sediments, not related to the leaded gasoline composition either. The continental input (1.18, 2.48) is highly influenced by precipitation, being difficult to separate both sources (atmosphere and continental runoff), showing also similar isotopic ratio to marine sediments. The signal of industrial emissions is masked with the introduction of Pb with higher isotopic ratios, compared to the values observed in the material collected from traps (SPM approximately 1.19, 2.48). The contribution of more radiogenic Pb by the upwelling is suggested.     

Trace element studies in Laucala Bay, Suva, Fiji.

The trace metal distribution in the sediments of Laucala Bay, a coastal lagoon with a barrier reef and significant freshwater input, adjacent to Suva, the capital of Fiji (150,000 people), was studied from the point of view of assessing the significance of anthropogenic sources relative to natural ones. Surface sediments from 25 sites in the Bay were analysed for particle size distribution, organic carbon and major (Si, Al, Fe, Ca, Mg) and trace metal (Mn, Zn, Cu, Pb, Cd, Hg) contents. Suspended sediments from one site and shellfish samples from five sites were also analysed. The sediments were found to be mostly of terrigenous origin. Particle size distribution, organic carbon and major elemental composition of the sediments were generally related to location within the Bay. A significant natural source of trace metals in the sediments is the suspended solids transported into the Bay by rivers. The spatial distribution of trace metals could not be fully explained by the particle size distribution and mineral composition of the sediments. Contributions from anthropogenic sources were also suspected, but the degree of enrichment from such sources is not great at the present time.     

Spatio-temporal variability of phytoplankton assemblages in the Pearl River estuary, with special reference to the influence of turbidity and temperature

The Pearl River Estuary is among the largest estuaries in the subtropical areas of the world. Along the salinity and turbidity gradient between the freshwater reach of the Pearl River and the marine water of the South China Sea, the spatial and temporal composition and abundance of phytoplankton was examined in relation to physic-chemical variables during the dry and wet seasons of 2009. Water samples for phytoplankton and environmental parameters were collected from 18 stations during two seasons along a transect from upper estuary to estuarine and marine sectors. A total of 162 species belonging to 7 phyla were identified, with diatoms dominated in both seasons while dinoflagellates proliferated in autumn. Two main clusters and three sub-clades under each main cluster corresponding to seasons and water sectors were defined with multivariate analysis (cluster and nMDS). Based on the species composition and abundance of phytoplankton, both seasonal and spatial variability were observed at a significant level (ANOSIM: season effect, R=0.896, P<0.01; station effect, R=0.463, P<0.01). The correlation analysis between biotic and abiotic variables indicated that instead of the “proverbial” anthropogenic nutrients loading and salinity gradient, the best 2-variable combination (temperature and turbidity) showed a significant effect on the pattern of phytoplankton assemblages (ρ_w=0.49, BIOENV analysis) between wet and dry seasons in the Pearl River Estuary. This result suggests that physical disturbance either natural or manmade is a more important factor in regulating the phytoplankton community structure within the hydrologically distinct zone of estuaries.     

Sorption of perfluorooctane sulfonate (PFOS) on marine sediments

Sorption of anionic perfluorooctane sulfonate (PFOS) on marine sediment was investigated in detail. It was found that solution ionic composition and sediment-specific parameters played important roles in affecting the sorption of PFOS. The results indicated that sorption of PFOS in seawater to marine sediments was strong (≈ 10 times higher than that in freshwater) and nonlinear (Freundlich n(F) values of 0.77-0.96). The sorption affinity was well correlated with sediment organic carbon content, indicating the importance of hydrophobic interactions. At a PFOS aqueous concentration of 10 μg/L, PFOS distribution coefficients increased with the increasing salinity in solution, with an average rate of 0.48 ± 0.03 log units per a log unit of salinity. Further studies demonstrated that among common ions contributing to the salinity in seawater, dissolved calcium and magnesium are dominantly responsible for the sorption-enhancing effect of salinity for PFOS. This work will aid in better understanding of PFOS sorption mechanisms, and be useful for fate modeling of this class of contaminants in the marine environment.     

Transitional and freshwater bioassessments: One site,two perspectives?

The freshwater–saltwater-transition-zone was analysed using two different sampling protocols and assessment methodologies, developed for freshwater and estuaries, to compare their agreement level in terms of community composition and quality assessments. The use of different protocols resulted in significant differences in macroinvertebrate communities, in index scores and initially in quality classes. After modifications in the sensitivity scores of the IBMWP and AMBI indices (average scores or the use of a score of the other index when both were present), the differences were largely reduced and quality classes became coincident for the assessments provided by IPtIs and BAT tools. Such harmonisation of quality assessments for adjacent water categories (e.g., large rivers vs. transitional waters), exemplified here as an harmonisation in one of the metrics comprised in the assessment tools, is essential as it has direct implications on the expansion and accomplishment of River Basin Management Plans committed by the Water Framework Directive.     

Adsorption behaviour of dibutyl phthalate on marine sediments

Laboratory experiments were carried out to investigate the adsorption behaviour of dibutyl phthalate (DBP) on marine sediments collected from five different sites in Victoria Harbour, Hong Kong. DBP adsorption can be well described by the Langmuir isotherm. The maximum DBP adsorption capacity (Q(max)) of the marine sediments ranges from 53 to 79 mg g(-1), which has a positive correlation with their organic content. Around 90% of the organic can be removed from the sediments with treatment by H(2)O(2) oxidation, and the Q(max) then decreases to a range between 13 and 22 mg g(-1). The black carbon content of the sediments has a much greater DBP adsorption capacity than does the natural organic matter of the sediments. The amount of DBP adsorbed on the sediments increases as the salinity of the marine water increases.     

Inter-annual variability of wet season freshwater plume extent into the Great Barrier Reef lagoon based on satellite coastal ocean colour observations

Riverine freshwater plumes are the major transport mechanism for nutrients, sediments and pollutants into the Great Barrier Reef (GBR) lagoon and connect the land with the receiving coastal and marine waters. Knowledge of the variability of the freshwater extent into the GBR lagoon is relevant for marine park management to develop strategies for improving ecosystem health and risk assessments. In this study, freshwater extent has been estimated for the entire GBR lagoon area from daily satellite observations of the Moderate Resolution Imaging Spectroradiometer (MODIS) between 2002 and 2010. To enable a reliable mapping of freshwater plumes we applied a physics-based coastal ocean colour algorithm, that simultaneously retrieves chlorophyll-a, non-algal particulate matter and coloured dissolved organic matter (CDOM), from which we used CDOM as a surrogate for salinity (S) for mapping the freshwater extent.     

Herbicides implicated as the cause of severe mangrove dieback in the Mackay region, NE Australia: consequences for marine plant habitats of the GBR World Heritage Area

Herbicides, particularly diuron, were correlated with severe and widespread dieback of the dominant mangrove, Avicennia marina (Forsk.) Vierh. var. eucalyptifolia (Val.) N.C. Duke (Avicenniaceae), its reduced canopy condition, and declines in seedling health within three neighbouring estuaries in the Mackay region of NE Australia. This unusual species-specific dieback, first observed in the early 1990s, had gotten notably worse by 2002 to affect >30 km(2) of mangroves in at least five adjacent estuaries in the region. Over the past century, agricultural production has responded well to the demands of increasing population with improvements in farm efficiency assisted by significant increases in the use of agricultural chemicals. However, with regular and episodic river flow events, these chemicals have sometimes found their way into estuarine and nearshore water and sediments where their effects on marine habitats have been largely unquantified. Investigations over the last three years in the Mackay region provide compelling evidence of diuron, and possibly other agricultural herbicides, as the most likely cause of the severe and widespread mangrove dieback. The likely consequences of such dieback included declines in coastal water quality with increased turbidity, nutrients and sediment deposition, as well as further dispersal of the toxic chemicals. The implications of such findings are immense since they describe not only the serious deterioration of protected and beneficial mangrove habitat but also the potential for significant direct and indirect effects on other highly-valued estuarine and marine habitats in the region, including seagrass beds and coral reefs of the Great Barrier Reef lagoon. This article reviews all key findings and observations to date and describes the essential correlative and causative evidence.     

What is the future fate of estuaries given nutrient over-enrichment,freshwater diversion and low flows?

Freshwater inflow is central to the definition of estuaries and if we lose control of the quantity of freshwater flow or discharge (including seasonal timing) to estuaries, then freshwater water quality has the potential to become a moot issue in estuarine ecosystems (Definition of estuaries: estuaries (aestus = tide) are physico-chemically, geomorphically, and biotically diverse ecosystems. Although numerous definitions of estuaries exist, we prefer the following: an estuary is a partially enclosed coastal water body in which freshwater runoff, often seasonally and episodically pulsed, dilutes salty ocean water and the biotic structure is influenced by dynamic tidal action and associated salinity gradients and reef building organisms and wetlands influence development and evolution of ecological structure and function (see for expanded definition)).     

Geochemistry of organic carbon and nitrogen in surface sediments of coastal Bohai Bay inferred from their ratios and stable isotopic signatures

Total organic carbon (TOC), total nitrogen (TN) and their δ(13)C and δ(15)N values were determined for 42 surface sediments from coastal Bohai Bay in order to determine the concentration and identify the source of organic matter. The sampling sites covered both the marine region of coastal Bohai Bay and the major rivers it connects with. More abundant TOC and TN in sediments from rivers than from the marine region reflect the situation that most of the terrestrial organic matter is deposited before it meets the sea. The spatial variation in δ(13)C and δ(15)N signatures implies that the input of organic matter from anthropogenic activities has a more significant influence on its distribution than that from natural processes. Taking the area as a whole, surface sediments in the marine region of coastal Bohai Bay are dominated by marine derived organic carbon, which on average accounts for 62±11% of TOC.     

Absence of β-alanine and γ-aminobutyric acid in cleaned foraminiferal shells: Implications for use as a chemical criterion to indicate removal of non-indigenous amino acid contaminants

The amino acids β-alanine and γ-aminobutyric acid are known to compose only a very minor proportion of the total amino acid content in living matter. In deep-sea sediments, however, their abundance in high proportions is ubiquitous. The organic material within foraminiferal calcite tests that are recovered from marine sediments has been found to contain no β-alanine and γ-aminobutyric acid. This observation provides a chemical check that can be used to ensure that the tests have been thoroughly cleaned. Such checks are important because the amino acid composition of organic material contained within the test is currently being used to establish schemes for chronology and taxonomy of foraminifera.